Catalyst for improving the performance of liquid hydrocarbon fuel

ABSTRACT

The present invention provides a method of making a catalyst for improving the performance of liquid hydrocarbon fuel. The treating agent for improving the performance of liquid hydrocarbon fuel is made by preparing a resin or a rubber composition having 100 parts by weight of a resin or a rubber component, 15 to 60 parts by weight of a carbon source having a particle size of not more than 0.5 mm and containing anthracite in amount not less than 62.5%, to 85 parts by weight of a silicon dioxide source having a particle size of not more 0,5 mm and containing quartz sand in an amount not less than 8-% and 5 to 15 parts by weight of glass fiber having an average fiber length of 6 to 12 μm, press molding the composition to obtain a molded article, and aging the molded article.

TECHNICAL FIELD

The present invention relates to a method of making a catalyst forliquid hydrocarbon fuel. More particularly, it relates to a method ofmaking a catalyst for liquid hydrocarbon fuel, which enhances combustionefficiency of fuel in internal-combustion engines, reduces an amount ofincomplete combustion materials in exhaust gas, and improves performanceof internal-combustion engines.

BACKGROUND ART

Hitherto, there has been serious problem in air pollution and harmfulinfluence on the Earth environment derived from exhaust gas ofinternal-combustion engines, such as an automobile. In order to lightenthe problem, many methods have been proposed, for example an improvementof a structure or combustion mode of internal-combustion engines, andemployment of a filter, a removal of an impurity in fuel and the like.However, some of them have made a sacrifice of the performance of theinternal-combustion engines. Then, as a method to clean exhaust gaswhile maintaining the performance of the internal-combustion engines,methods of reducing a content of incomplete combustion materials in theexhaust gas by improving the combustion efficiency of fuel have beenproposed. The methods include an elevation of a combustion temperatureof fuel, a removal of an impurity during a purification step of fuel, anincrease of an octane number of fuels by an addition of additives orchemical reaction, and the like. However, the methods mentioned abovegenerally make complicate productive facilities and manufacturingprocess, and are not practiced with ease and at low cost.

DISCLOSURE OF INVENTION PROBLEM TO BE SOLVED BY THE INVENTION

A main object of the present invention is to provide a method of makinga catalyst for liquid hydrocarbon fuel. The catalyst improves combustionefficiency of fuel for internal-combustion engines with ease and at lowcost.

MEANS FOR SOLVING THE PROBLEM

The present inventors have intensively studied to attain the abovementioned object and have found that a resin or rubber compositioncontaining specified amounts or carbon-containing powder and silicondioxide-containing powder is press-molded to form a catalyst which canbe prepared at low cost with ease and surprisingly increases acombustion efficiency of fuel in internal-combustion engines. Thus, thepresent invention has been completed.

The present invention relates to a method of making a catalyst forliquid hydrocarbon fuel comprising the steps of:

(a) preparing a resin or rubber composition comprising

(i) 100 parts by weight of a resin or rubber component;

(ii) 15 to 60 parts by weight of a carbon source having a particle sizeof not more than 0.5 mm and containing anthracite of not less than62.5%;

(iii) 35 to 85 parts by weight of a silicon dioxide source having aparticle size of not more than 0.5 mm and containing quartz sand of notless than 80 %; and

(iv) 5 to 15 parts by weight of glass fiber having an average fiberlength of 6 to 12 μm;

(b) press molding the composition to obtain a molded article, and

(c) aging the molded article.

The present invention also relates to a method of making a catalyst forliquid hydrocarbon fuel comprising the steps of:

(a) preparing a resin or rubber composition comprising

(i) 100 parts by weight of a resin or rubber component;

(ii) 15 to 60 parts by weight of a carbon source having a particle sizeof not more than 0.5 mm and containing anthracite of not less than62.5%;

(iii) 35 to 85 parts by weight of a silicon dioxide source having aparticle size of not more than 0.5 mm and containing quartz sand of notless than 80%;

(iv) 5 to 15 parts by weight of glass fiber having an average fiberlength of 6 to 12 μm; and

(v) 5 to 15 parts by weight of tungsten powder having a particle size ofnot more than 0.2 mm;

(b) press molding the composition to obtain a molded article, and

(c) aging the molded article.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a schematic cross section illustrating one embodiment of adevice containing the catalyst for liquid hydrocarbon fuel of thepresent invention.

FIG. 2 is a schematic cross section illustrating one embodiment of themold which is used for the method of making the catalyst for liquidhydrocarbon fuel of the present invention.

FIG. 3 is a schematic drawing illustrating a device which is used for aburning test in Examples of the present invention.

The resin or rubber composition used for the present invention comprisesa resin or rubber component, a carbon source, a silicon dioxide source,glass fiber and the like. The resin or rubber component used for thepresent invention is not limited as long as it has sufficient heatresistance to use at a temperature for working the catalyst for liquidhydrocarbon fuel of the present invention (40° to 100° C.), and it isinsoluble in the liquid hydrocarbon fuel to be used. Examples of theresin or rubber component include thermosetting resins, such as phenolresin, epoxy resin, melamine resin and the like; thermoplastic resins,such as polyethylene, polypropylene, poly(vinyl chloride), polystyreneand the like; natural rubber; synthetic rubber, such as butadienerubber, isoprene rubber, acrylic rubber, urethane rubber, siliconerubber, fluororubber and the like. Typical examples of the resincomponents include phenol resin “F-2410” (trade name), which iscommercially available from Food Co., Ltd.; “Estar H8100”, “EstarH6650PC”, “Estar R-3115B” (trade name), which are commercially availablefrom Mitsui Toatsu Chemical Co., Ltd., and the like. Typical examples ofthe rubber compnenets include nitrile rubber, which is commerciallyavailable from Nippon Zeon Co., Ltd. under the trade name of“Epichlorohydrin CHR”, and the like.

The carbon source used for the present invention is not limited, butincludes simple substance of carbon, such as diamond, graphite and thelike; coal, such as anthracite, bituminous coal and the like; metalliccarbonate, such as limestone, dolomite and the like; and mixturesthereof. It is required that the carbon source used for the presentinvention contains not less than 62.5% by weight, preferably 75 to 80%by weight of anthracite having a carbon content of not less than 90%,based on the total weight of the carbon source. When the content of theanthracite is smaller than 62.5% by weight, the content of impurities istoo high and the impurities are oxidized to expand or corrode whencontacting with the hydrocarbon fuel. The carbon source has a particlesize of not more than 0.5 mm, preferably not more than 0.2 mm. When theparticle size is larger than 0.5 mm, the surface area of the carbonsource is too samll, and the technical effects accomplished by thepresence of the carbon source are not sufficiently obtained. The amountof the carbon source is 15 to 60 parts by weight, preferably 30 to 41parts by weight, based on 100 parts by weight of the resin or rubbercomponent. When the amount of the carbon source is smaller than 15 partsby weight, the technical effects accomplished by the presence of thecarbon source are not sufficiently obtained. On the other hand, theamount of the carbon source is larger than 60 parts by weight, a meltingviscosity of the resin or rubber composition at the time of pressmolding is high, and moldability is degraded. Therefore the technicaleffects accomplished by the presence of the carhon source are notfurther obtained.

The silicon dioxide source used for the present invention includesquartz, tridymite, cristobalite, coesite, stishovite, amorphous silica,quartz sand and the like, and mixtures thereof. It is required that thesilicon dioxide source used for the present invention contains not lessthan 80% by weight, preferable 90 to 95% by weight of quartz sand, basedon the total weight of the silicon dioxide source. When the content ofthe quartz sand is smaller then 80% by weight, the content ofimpurities, such as slime, iron oxide and the like are high. The silicondioxide source has a particle size of not more than 0.5 mm, preferably0.3 to 0.1 mm. When the particle size of the silicon dioxide source islarger than 0.5 mm, the surface area of the silicon dioxide source istoo small, and the technical effects accomplished by the presence of thesilicon dioxide source are not sufficiently obtained.

The amount of the silicon dioxide source is 35 to 85 parts by weight,preferably 60 to 81 parts by weight, based on 100 parts by weight of theresin or rubber component. When the amount of the silicon dioxide sourdeis smaller than 35 parts by weight, the technical effects accomplishedby the presence of the silicon dioxide source are not sufficientlyobtained. On the other hand, when the amount of the silicon dioxidesource is larger than 85 parts by weight, the melting viscosity of theresin or rubber composition at the time of press molding is high. andthe moldability is degraded. Therefore the technical effectsaccomplished by the presence of the silicon dioxide source are notfurther obtained.

The glass fiber used for the present invention may be one, which hasbeen typically used for glass fiber reinforced plastic and the like. Theglass fiber has a fiber diameter of 1 to 1.5 μm, preferably 1 to 1.2 μm,and a fiber length of 6 to 12 μm, preferably 6 to 8 μm. The amount ofthe glass fiber is 5 to 15 parts by weight, preferably 10 to 12 parts byweight, based on 100 parts by wieght of the resin or rubber component.When the amount of the glass fiber is smaller than 5 parts by weight,the resulting molded article does not have sufficient strength, and haschips or cracks when producing and using it. On the other hand, when theamount of the glass fiber is larger than 15 parts by weight, a weightratio of resin or rubber component in the molded article is too low, andmoldability is degraded.

In another embodiment of the present invention, the resin or rubbercomposition further contains tungsten powder, in addition to thecomponents described above. The tungsten powder used for the presentinvention may be one having a purity content of not less than 80%, whichhas been commercially available for industrial use. The tungsten powderhas a particle size of not more than 0.2 mm, preferably not more than0.1 mm. When the particle size of the tungsten powder is larger than 0.2mm, the surface area of the tungsten powder is too small, and thetechnical effects accomplished by the presence of the tungsten powderare not sufficiently obtained. The amount of the tungsten powder is 5 to15 parts by weight, preferably 7 to 12 parts by weight, based on 100parts by weight of the resin or rubber component. When the amount of thetungsten powder is smaller than 5 parts by weight, the technical effectsaccomplished by the presence of the tungsten powder are not sufficientlyobtained. On the other hand, when the amount of the tungsten powder islarger than 15 parts by weight, the technical effects accomplished bythe presence of the tungsten powder are not further obtained. In case ofusing a hydrocarbon fuel having a specific gravity of not less than 0.8for the internal-combustion engine, the catalytic effects are notsufficiently obtained by using only the carbon source and silicondioxide as a catalyst, because the temperature and consumption of thehydrocarbon fuel increase with the increase of the engine speed. The useof the tungsten powder in the resin or rubber composition compensatesfor the insufficiency of the catalytic effect.

The composition of the present invention may be prepared by blending theformulation components with a blender, which has been typically used forblending resin compositions and the like. In order to accomplish uniformblend, the formulation components other than the resin or rubbercomponent may be blended in advance, and then adding the resin or rubbercomponent thereto to blend them together. In order to improve thedispersibility of the powders and glass fiber in the resin or rubbercomponent, the formulation components may be further mixed by a mixersuch as a mixing roll, which has been typically used for the purpose inconsideration of the difference in specific gravity.

The composition is then molded into sphere by press molding in a molddescribed in FIG. 2 at 130° to 250° C. and 70 to 200 Kgf/cm² for 20 to40 minutes, and then the molded articles are left to stand until coolingto room temperature. The press molding is conducted at the condition of200° to 250° C., 70 to 90 Kgf/cm² for 30 to 40 minutes when using theresin component, and at the condition of 130° to 150° C. for 20 to 30minutes under the pressure which has been typically used for moldingrubber when using the rubber component. FIG. 2 is a schematic crosssection illustrating one embodiment of the mold used for the method ofmaking the catalyst for liquid hydrocarbon fuel of the presentinvention. The mold is composed of the upper mold 4 and the lower moldr. Optionally, about 6,000 particles of the molded articles 3 are put ina 30 liter-ball mill and milled at a number of revolution of 8 to 10 rpmfor 1 to 1.5 hours without using a grinding medium for deflashing toobtain spherical molded articles having a diameter of 8.9 to 9 mm. Thecatalyst for liquid hydrocarbon fuel is produced by leaving the moldedarticles to stand at room temperature in a dark place with naturaldrafting for 3 to 4 weeks and then washing with water, followed bydrying by sunlight for 2 to 3 days. For example, 30 to 60 particles ofthe resulting liquid hydrocarbon fuel catalysts 1 are put in a container2 shown in FIG. 1 when using for the internal-combustion engine having adisplacement of 2,000 to 2,500 cc, to obtain a device containing thecatalyst for liquid hydrocarbon fuel of the present invention. FIG. 1 isa schematic cross section illustrating one embodiment of the devicecontaining the catalyst for liquid hydrocarbon fuel of the presentinvention. Liquid hydrocarbon fuel having good combustion efficiency canbe obtained with ease and at low cost by passing liquid hydrocarbon fuelthrough the container having the catalysts obtained by the method of thepresent invention. The shape of the catalyst of the present invention ispreferably spherical in view of the surface area, but may be tabular orirregular.

The present invention provides a method of making a catalyst for liquidhydrocarbon fuel, which improves combustion efficiency of fuel ininternal-combusion engines with ease and at low cost.

EXAMPLES

The following Examples and Comparative Examples further illustrate thepresent invention in detail but are not to be construed to limit thescope of the present invention.

Preparation of resin composition

The following components were mixed to obtain a resin composition:

(i) 100 parts by weight of phenol resin (“F-2410” commercially availablefrom Food Co., Ltd.)

(ii) 60 parts by weight of carbon source (content of anthracite: 70%,particle size: not more than 0.3 mm)

(iii) 75 parts by weight of silicon dioxide source (content of quartzsand: 80%, particle size: not more than 0.5 mm), and

(iv) 15 parts by weight of glass fiber (fiber diameter: 1 to 1.2 μm,fiber length: 6 to 10 μm).

Production of catalyst for liquid hydrocarbon fuel

The resulting resin composition was press molded in the mold shown inFIG. w at 240° C. for 30 minutes, and Then the molded articles were leftto stand until cooling to room temperature. About 6,000 particles of theresulting molded articles were put in a 30 liter-ball mill, and milledat the number of revolution of 10 rpm for 1.5 hours without using agrinding medium for deflashing, to obtain spherical resin moldedarticles having a diameter of 9 mm. The catalyst for liquid hydrocarbonfuel was produced by aging the molded articles at room temperature in adark place with natural drafting for 3 weeks, and washing with water,followed by drying by sunlight for 2 days. 40 particles of the resultingliquid hydrocarbon fuel catalysts 1 were put in a container 3 shown inFIG. 1 to obtain a catalyst device for liquid hydrocarbon fuel.

EXAMPLE

A burning test of illuminating kerosine passed through the catalystdevice for liquid hydrocarbon fuel was conducted. The result is shown inTable 2. After the catalyst device for liquid hydrocarbon fuel was mounton a diesel engine car and gasoline engine car (between the engine andfuel tank), the exhaust gas analysis and horsepower test of the bothcars, and the combustion efficiency test of the gasoline engine car(10-mode and normal running at 60 km/h) were conducted. The results areshown in Tables 3, 4 and 5. The test methods are described later.

COMPARATIVE EXAMPLE

A burning test of illuminating kerosine, the exhaust gas analysis andhorsepower test of the diesel engine car and gasoline engine car, andthe combustion efficiency test of the gasoline engine car (10-mode andnormal running at 60 km/h) were conducted as described in Example,except that the catalyst device for liquid hydrocarbon fuel was notused. The results are shown in Tables 2, 3, 4 and 5.

(Test method)

(1) Burning test

After illuminating kerosine 6 in a alcohol lamp 7 was burned for 15minutes using a burning test device shown in FIG. 3 at a roomtemperature of 12° C. and water temperature of 9.5° C., an average oftemperature change of tap water 10 in a beaker 9 on a chassis havinglegs 11 is measured using a thermometer 8 for every two samples (n=2).

(2) Exhaust gas analysis

A content of carbon oxide and hydrocarbon in exhaust gas when letting agasoline engine idle were measured using a CO, HC analyzer, “MEXA324G”manufactured from Horiba Co., Ltd., and a content of black smoke inexhaust gas when a diesel engine was open all the way for 4 seconds inneutral gear was measured using a black smoke tester manufactured byBanzai Co. Ltd.

(3) Horsepower test

Maximum horsepowers of a gasoline engine car and diesel engine car weremeasured using an IYASAKA vehicle Performance Tester VFT-7048WY. Theresults were corrected to a value at an atmospheric pressure of 1013 mband an atmospheric temperature of 20° C. The car used for the test isshown in Table 1.

(4) Fuel efficiency

The fuel efficiency of the gasoline engine car under the condition of10-mode and normal running at 60 km/h. The car used for the test isshown in Table 1.

TABLE 1 Gasoline Diesel engine Test vehicle engine car car Type of carMazda Luce Mazda Friendee V6 (V-six) Diesel Turbo (E-HCFS) AT* (KD-SGL3)AT* 1889 model 1996 model Gross vehicle weight(kg) 1450 1770 Dimensionsof length 469 458 vehicle (cm) width 169 169 height 139 209 Type ofengine Gasoline Diesel Displacement (cc) 2000 2500 Ignition type NormalNormal ignition ignition Wheelbase (cm) 2710 2910 *Automatictransmission

TABLE 2 Comparative Test item Example Example Water temperature 9.5 9.5before burning (° C.) Water temperature after 86.5 67.0 burning (° C.)Difference in the 77.0 57.5 temperature (° C.)

TABLE 3 Diesel engine car Gasoline engine car Comparative ComparativeTest item Example Example Example Example Content of — — 0 0.05 CO (%)Content of — — 18 65 HC (ppm) Content of 32.0 32.7 — — black smoke (%)

TABLE 4 Diesel engine car Gasoline engine car Comparative ComparativeTest item Example Example Example Example Maximum 107.0 101.0 112.0 99.0horsepower (hp) Vehicle 102.0 92.0 99.0 99.0 velocity at maximumhorsepower (km/h) Engine speed 1 1 1 1 at maximum horsepower (rpm)

TABLE 5 Comparative Test item Example Example (10-mode) Running time(sec) 134.9 134.9 Running distance (m) 688 684 Fuel Consumption (ml) 94121 Average fuel consumption 7.32 5.65 ratio (km/l) (Normal running at60 km/h) Average vehicle velocity 62.1 61.9 (km/h) Average load (kg)21.4 24.1 Running distance (m) 3001 3003 Fuel Consumption (ml) 262 314Average fuel consumption 11.45 9.56 ratio (km/l)

As is apparent from the results described above, the liquid hydrocarbonfuel of Example passed through the liquid hydrocarbon fuel catalystdevice of the present invention has large increase of a temperature oftap water in the burning test when compared with that of ComparativeExample which is not passed through the devide, and the combustionefficiency is improved. The liquid hydrocarbon fuel of Example has lowercontent of carbon oxide and hydrocarbon in exhaust gas from the gasolineengine car, and lower content of black smoke in exhaust gas from thediesel engine car than that of Comparative Example.

In the performance of the internal-combustion engine, the maximumhorsepower of both gasoline and diesel engine car are large, and thefuel efficiency of the gasoline engine car increases, by using theliquid hydrocarbon fuel catalyst of the present invention.

It is apparent that the combustion efficiency of the liquid hydrocarbonfuel is improved, and the content of incomplete combustion materials inexhaust gas reduces, by using the liquid hydrocarbon fuel catalyst ofthe present invention, which improves the performance of theinternal-combustion engine.

EFFECT OF INVENTION

The combustion efficiency of the liquid hydrocarbon fuel increases, andthe content of incomplete combustion materials in the exhaust gasreduces, by using the liquid hydrocarbon fuel catalyst obtained usingthe method of the present invention, thus improving performance ofinternal-combustion engines.

What is claimed is:
 1. A method of making a catalyst improving theperformance of liquid hydrocarbon fuel comprising the steps of: (a)preparing a resin or rubber composition comprising (i) 100 parts byweight of a resin or rubber component; (ii) 15 to 60 parts by weight ofa carbon source having a particle size of not more than 0.5 mm andcontaining anthracite in an amount not less than 62.5%; (ii) 35 to 85parts by weight of a silicon dioxide source having a particle size ofnot more than 0.5 mm and containing quartz sand in an amount not lessthan 80%; and (iv) 5 to 15 parts by weight of glass fiber having anaverage length of 6 to 12 μm; (b) press moding the composition to obtaina molded article, and (c) aging the molded article.
 2. The method ofmaking a catalyst for improving the performance of liquid hydrocarbonfuel according to claim 1, wherein the composition further comprises 5to 15 parts by weight of tungsten powder having a particle size of notmore than 0.2 mm, based on 100 parts by weight of the resin or rubbercomponent.
 3. The method of making a catalyst for improving theperformance of liquid hydrocarbon fuel according to claim 1, wherein thestep (a) of preparing the composition is conducted by mixing thecomponents (ii), (iii) and (iv), and then adding the component (i)thereto and mixing.
 4. The method of making a catalyst for improving theperformance of liquid hydrocarbon fuel according to claim 1, wherein thepress molding step (b) is conducted at 130° to 250° C. for 20 to 40minutes.
 5. The method of making a catalyst for improving theperformance of liquid hydrocarbon fuel according to claim 1, wherein theaging step (c) is conducted by letting the molded article stand at roomtemperature in a dark place under normal atmospheric conditions for 3 to4 weeks, and then washing with water, followed by drying in sunlight for2 to 3 days.